This invention relates to novel processes for preparing, pesticides or pesticidal intermediates (particularly 5-amino-1-aryl-3-cyanopyrazole derivatives).
European Patent Publication Nos. 0295117 and 0234119 describe the preparation of pesticidally active phenylpyrazole compounds and of 5-amino-1-aryl-3-cyanopyrazole intermediate compounds used in their synthesis.
Various methods for preparing these compounds are known. The present invention seeks to provide improved or more economical methods for the preparation of pesticides and the intermediate compounds useful in preparing them.
It is a first object of the present invention to provide a convenient process for preparing pesticidally active phenylpyrazole compounds or 5-amino-1-aryl-3-cyanopyrazole pesticidal intermediates, which are obtained in high yield and high purity.
It is a second object of the present invention to provide a convenient process for preparing pesticidally active phenylpyrazole compounds or 5-amino-1-aryl-3-cyanopyrazole pesticidal intermediates, which proceeds without the need for a diazotisation step and hence avoids problems such as hazards known to occur for such reactions.
It is a third object of the present invention to provide a process for preparing pesticidally active phenylpyrazole compounds or 5-amino-1-aryl-3-cyanopyrazole pesticidal intermediates, which is simple to perform and uses less expensive starting materials than known methods.
It is a still further object of the present invention to provide novel intermediates in the manufacture of pesticidally active compounds.
These and other objects of the invention will become apparent from the following description, and are achieved in whole or in part by the present invention.
The present invention accordingly provides a process (A) for the preparation of a compound of formula (I): 
wherein W represents nitrogen or xe2x80x94CR4;
R1 represents halogen, haloalkyl (preferably trifluoromethyl), haloalkoxy (preferably trifluoromethoxy), R5S(O)nxe2x80x94, or xe2x80x94SF5;
R2 represents hydrogen or halogen (for example chlorine or bromine);
R3 represents hydrogen or R6S(O)mxe2x80x94;
R4 represents halogen (for example chlorine or bromine);
R5 and R6 represent alkyl or haloalkyl; and
m and n represent 0, 1 or 2; which process comprises the reaction of a compound of formula (II): 
xe2x80x83wherein R1, R2, R3 and W are as hereinbefore defined, R7 represents a leaving group (preferably chlorine or bromine) and R8 represents chlorine or bromine (preferably R7 and R8 each represent chlorine), with a cyanide salt. The reaction proceeds via dicyano intermediates of formula (III): 
xe2x80x83wherein R1, R2, R3 and W are as hereinbefore defined, which generally cyclise under the conditions of the reaction, thus providing a simple and convenient process. Optionally the intermediates of formula (III) may be cyclised in the presence of base according to known methods. Compounds of formula (II) and (III) may exist as a mixture of syn and anti isomers.
Unless otherwise specified in the present specification xe2x80x98alkylxe2x80x99 means straight- or branched-chain alkyl having from one to six carbon atoms (preferably one to three). Unless otherwise specified xe2x80x98haloalkylxe2x80x99 and xe2x80x98haloalkoxyxe2x80x99 are straight- or branched-chain alkyl or alkoxy respectively having from one to six carbon atoms (preferably one to three) substituted by one or more halogen atoms selected from fluorine, chlorine or bromine.
Suitable cyanide salts for the above reaction to form compounds of formula (I) include alkali metal cyanides such as potassium, sodium or lithium cyanide, alkaline earth metal cyanides or ammonium cyanide. Potassium cyanide or sodium cyanide are preferred. The reaction is generally conducted in a solvent. Solvents suitable for use include nitriles such as acetonitrile, amides such as N-methylpyrrolidinone, sulphoxides such as dimethylsulphoxide, ethers such as tetrahydrofuran or alcohols such as ethanol. Water may be employed as a co-solvent. The reaction temperature is generally from about xe2x88x9220xc2x0 C. to the reflux temperature of the solvent, and preferably from about 0xc2x0 C. to about 20xc2x0 C.
Generally from two to 5 molar equivalents of cyanide and preferably from about two to about three equivalents are employed.
In formulae (I), (II) and (III) and in the formulae depicted hereinafter, preferred values of the symbols are as follows:
R1 represents haloalkyl (preferably trifluoromethyl), haloalkoxy (preferably trifluoromethoxy) or xe2x80x94SF5;
W represents xe2x80x94CR4;
R2 and R4 represent halogen (preferably chlorine);
R3 represents a hydrogen atom, or R6S(O)mxe2x80x94; wherein R6 represents optionally halogenated methyl or ethyl (preferably trifluoromethyl); and R7 and R8 represent chlorine.
Particularly preferred compounds of formula (I) include:
5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole;
5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole;
5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulphinylpyrazole; and
5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-ethylsulphinylpyrazole.
The process is particularly useful for preparing compounds in which R3 represents hydrogen, and most preferably for 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole.
In formulae (II) and (III) and in the formulae depicted hereinafter, the most preferred values of the symbols are as follows:
R1 represents trifluoromethyl;
W represents xe2x80x94CR4;
R2, R4, R7 and R8 represent chlorine; and
R3 represents hydrogen.
According to a further feature of the present invention the above process (A) can be combined with additional process steps (B) and (C) as defined hereinbelow.
Process step (B); comprises the reaction of a compound of formula (IV): 
wherein R1, R2, R3, p7 and W are as hereinbefore defined, with a chlorinating or brominating agent; to give a compound of formula (II) wherein R1, R2, R3, R7, R8 and W are as hereinbefore defined.
Suitable chlorinating agents are thionyl chloride, phosphoryl chloride, phosphorus trichloride, phosphorus pentachloride or a mixture of triphenylphosphine and carbon tetrachloride. Brominating agents which may be used include thionyl bromide, phosphoryl bromide or a mixture of triphenylphosphine and carbon tetrabromide. Preferably the process is performed using a chlorinating agent. A preferred chlorinating agent is phosphoryl chloride.
Solvents which may be used include ethers, aromatic hydrocarbons such as toluene, aromatic halogenated hydrocarbons such as chlorobenzene, or halogenated hydrocarbons such as dichloroethane.
The reaction temperature is generally from 0xc2x0 C. to 120xc2x0 C., preferably from 70xc2x0 C. to 90xc2x0 C.
Process step (C) comprises the reaction of an arylhydrazine compound of formula (V): 
wherein R1, R2 and W are as hereinbefore defined; with a compound of formula (VI):
R3R7CHCOR9xe2x80x83xe2x80x83(VI)
wherein R3 and R7 are as defined above, and R9 represents a leaving group preferably a chlorine or bromine atom (generally both R7 and R9 represent a chlorine atom); to give a compound of formula (IV) as defined above. The reaction to obtain compounds of formula (IV) is generally performed in a solvent such as halogenated hydrocarbons for example dichloromethane, ethers for example tetrahydrofuran or dioxan, or N,N-dialkylamides for example N,N-dimethylformamamide, and at a temperature of from xe2x88x9220xc2x0 to 50xc2x0 C., preferably from 0 to 20xc2x0 C.
The above combination of process step (A), preceded by process step (B), preceded by process step (C), represents in certain aspects an improvement over the prior art.
Compounds of formula (II) and (IV) above are novel and therefore constitute a further feature of the present invention.
Where R3 is other than hydrogen, compounds of formula (III) are novel.
Compounds of formula (VI) are known.
The intermediate 5-amino-1-aryl-3-cyanopyrazole compounds of formula (I) obtained by the process (A) of the invention wherein R3 represents hydrogen, may be used in the preparation of pesticidally active phenylpyrazole derivatives of formula (VII) according to the following reaction scheme: 
wherein the symbols used above are as hereinbefore defined.